Xsoih



' radical which may be substituted. '7

United States Patent i DYESTUFFS OF THE ANTHRAPYRIDONE 'ANDANTHRAPYRIDINE SERIES COMPRISING A HALOGENATED TRIAZINYL GROUP JacquesGuenthard, Basel, Switzerland, assignor to Sandoz Ltd., Basel,Switzerland No Drawing. Filed Jan. 29, 1959, Ser. No. 790,318

: Claims priority, application Switzerland Jan. 31, 1958 Claims. (Cl.260-249) The present invention relates to dyestuffs of the anthraquinoneseries which contain reactive groups and correspond to the formula R2 6N l! 1 (I) NH-Rr-N SOaH R wherein R stands for a halogeno aeetylradical, a halogenapropionyl radical or the radical of a cyclic,six-membered triazine compound containing two halogen atoms attached tocarbon atoms,

A for hydrogen or a low molecular alkyl radical,

R for a phenylene or diphenylene radical which contains the group inpara-position to the NH group,

R for a low molecular canbalkoxy radical, a low molecu lar alkylcarbonylradical, or a phenylcarbonyl radical Y which may be substituted,

and

R for the hydroxy group, a low molecular alkyl'radical or a phenylradical which may be substituted, when R stands for a low molecularcarbalkoxy radical, but only for the hydroxy group when R stands for alow molecular alkylcarbonyl radical. -or va.-phenylca rbonyl PatentedNov. 29, 1960 The process for their production consists in reacting 1mole of a dyestufi of the formula SOiH wherein A, R and R possess theaforecited meanings and v I R stands for a phenylene or diphenyleneradical which contains the NH-A group in para-position to the NH group,

with 1 mole of a functional derivative of a halogeno acetic or ahalogenopropionic acid or with 1 mole of a cyclic, six-membered triazinecompound containing three halogen atoms attached to carbon atoms.

The dystufis of Formula II which are used as starting substances are3-azabenzanthrone derivatives and are pro duced by the known methods. Rdenotes preferably a carbomethoxy, carbethoxy, acetyl or benzoyl group,when R is a hydroxy group, but its meaning is restricted to acarbomethoxy or carbethoxy group when R is a methyl or phenyl group.Especially interesting representatives are, e.g.,

Q-fl'the functional derivatives of a halogeno aceticor halogenopropionicacid preference is given to the a'nhyldride 'and the chloride ofchloroacetic and fi-chloropropion' ic acid, while cyanuric chloride canbe taken an example of the triazine compounds coming within the scopeof'the' process.

The reaction of the dyestuffs of Formula II used as starting substanceswith a functional derivative of a halogeno acetic or halogenopropionicacid or a cyclic, sixmembered triazine compound containing three halogenatoms attached to carbon atoms is conducted preferably in aqueousmedium. The functional halogeno acetic or halogenopropionic acidderivative or the trihalogenotriazine compound can be employed as suchin concentrated form or, if desired, in solution in an organic solvent.Acetone is a specially suitable solvent for this purpose.

The reaction temperature is adjusted to the reactivity of theindividual'starting substances and varies-between and 100 C. If it isdesirable .to effect the'reaction at temperatures higher than 50-60 C.,e.g. with a halogeno acetic anhydride, it is advisable to work in closedvessels equipped with reflux condensers.

The reaction is carried out in a weakly alkaline, neutral to weakly acidmedium, but preferably within the pH region of 10.0 to 3.0. Toneutralise the hydrogen halide which may be formed, an acid-bindingagent such as sodium acetate or ammonium acetate can be added to thereaction solution at the start of the operation, or during the reactionsmall portions of sodium or potassium carbonate or bicarbonate in solid,powdered form as a concentrated aqueous solution can be added. Othersuitable neutralizing agents are aqueous solutions of sodium orpotassium hydroxide. The addition of small amounts of a wetting oremulsifying agent to the reaction mixture can accelerate the rate ofreaction.

In the reaction of functional derivatives of a halogeno acetic orhalogenopropionic acid with the free amino group a halogeno acetylaminoor halogenopropiony-lamino group is formed. In the reaction of atrihalogenortriazine compound with the free amino group only one halogenatom reacts with an exchangeable hydrogen atom.

On completion of condensation the dyestuif is'salted out of the solutionor suspension, which may be previously neutralized if desired, withsodium or potassium chloride or precipitated with acid. The precipitateis filtered with suction, washed until a neutral reaction is obtained,and finally dried.

The dyestuffs obtained in accordance with the invention are suitable fordyeing, padding and printing fibers of animal and vegetable origin,fibers of regenerated cellulose, casein fibers, animalized cellulosefibers, polyamide fibers, mixtures of the preceding fibers, and leather.The material is treated during or after dyeing with agents of alkalinereaction in a warm liquid or gaseous medium. The dyeings thus producedpossess good fastness to light, washing, milling, and perspiration.

In the following examples the parts and percentages are by weight andthe temperatures are in degrees centi-grade.

EXAMPLE 1 27.75 parts of the dyestuff 1-acetyl-2-hydroxy-6-(4- amino)phenylamino 3 azabenzanthrone 4.2 disulfonic acid are dissolved in 1000parts of water, and about 15 parts of a 30% sodium hydroxide. solution.After the addition of 9.3 parts of cyanuric chloride and drops of 'acommercial sulfonated fatty acid ester, the emulsion is vigorouslystirred at 0-5. Small portions of potassium carbonate are added tomaintain the pH value between 6.0 and 8.0. When the condensationreaction has run its course 50 parts of potassium chloride are strewnin,- causing the new dyestuff to be precipitated from the solution. Itis filtered 01f, washed with a dilute aqueous solution of potassiumchloride, and dried in vacuo at 5060. The

.dark. powder obtained dissolves in water to give violet-red solutions.When it is padded on cellulosic fiber fabrics from aqueous solution andsubsequently heat-treated in the presence of an agent of alkalinereaction, violet-red dye- 'ingsare obtained "which are fast to light andwet" agencies.

4 EXAMPLE 2 35.25 parts of the dyestuff sodium l-carbethoxy-Z-hydroxy 6[4' (4" amino) phenyl] phenylamino-3- azabenzanthrone-4.Z disuIfonateare dissolved in 1000 parts of water at 50.

The solution is cooled to 20 with simultaneous dropwise addition of 14parts of chloroacetyl chloride and, in the course of 30 minutes, theamount of 30% sodium hydroxide solution required to maintain a pH valueof 8.0 to 9.0. The mass is stirred for some time longer until thestarting substance is no longer indicated by chromatography of asamplevon a talc column.

The dyestulf is precipitated by means of 60 parts of common salt,filtered oif and dried. On grinding it is obtained as a powder which issoluble in water, giving violet-red solutions. Padded from aqueoussolution on cellulosic-fibers and subjected to an alkalineheat-treatment, the dyestufi yields violet. shades which'are. fast'tolight and wet treatments.

parts of" cotton sateen are padded at'room temperature with a 2% neutralaqueous solution of the above dyestufl in presence of 1 gram per literof turkey red oil. The padded fabric is squeezed to give an increase of60% to over the dry weight. While still moist it is entered in adeveloping bath (liquor to goods ratio 50:1) which contains 300 gramsper liter of common salt and 5 ml. per liter of sodium hydroxidesolution of 66 Tw. It-is treated in this bath for 20--30v minutes at90-.-95,- then thoroughly rinsed in .cold water, and soaped at the boilfor 20 minutes with'additions 015.5 grams per liter of soap and 2 gramsper liter of sodium bicarbonate (liquor ratio 20:1). After a furtherthorough rinse the dyed fabric is dried.

EXAMPLE 3 29.15 parts ofl-carbethoxy-2-methyl-6-(4'-methylamino)-phenylamino-3azabenzanthrone-4.2'-disulfonicacid are dissolved in 600 parts ofwater and 14 parts of 30% sodiumhydroxide solution at 50. .At this temperature small portions of meltedchloroacetic anhydride are dropped in, together with sufficient sodiumbicarbonate to give a constant pH of 6.0-7.0. The reaction is completedwhen the starting substance is no longer indicated in a sample. Thedyestuif is precipitated with 60 parts of sodium chloride and filteredoff; the filter cake is washed with brine until of neutral reaction andthen dried and ground. The powder obtained dissolves in water with anorange-red coloration; applied from weakly alkaline dyebaths, it dyesfibers of natural or regenerated cellulose in o-range-redshades whichare'fast to lightand wet agencies.

In the following table are listed further dyestufis containing reactivegroups which are obtainable according to the process described inExamples 1 to 3. They have the formula and -SO H groups in the radical Rand the shade of their dyeings on cotton.

9,962,497! 7 8. Example 26 3. The dyestufl of the formfila 11 EH: H n heODE-f N SOIH' 10 /CHa N c( CCl c C-Cl 8 ml 1 11 'SOIHv l- =l| N N N N 15C i .61 CI 4. The dyestuflf of the formula (711: "Having thus disclosedthe invention what I claim is: l. The dyestuff of the formulaHgCr-OOC-fi N c -C-Cl B OaH I ll 'N\ /N F H 61 5. Adye'smfioftheiormula:

N-C 0-c1 ll 1 u N N BOIH wherein A is selected from-the group consistingof hydrogen and methyl, R is selected from the group consisting of lowercarbalkoxy and benzoyl, R is selected from the groupconsistingofhydroxy, methyl and phenyl, and n is a numeral-ranging from0m 1.

References Cited in-the file of this patent UNITED STATES PATENTS2,759,939 Bucheler et al. Aug. 21, 1956 UNITED STATES PATENT OFFICECERTIFICATION OF CORRECTION Patent No. 2962,49? November 29 1960 JacquesGuenthard It is hereby certified that error appears in the abovenumbered patent requiring correction and that the said Letters Patentshould read as corrected below'.

Column 2 line 532 for "dystuffs read dyestuffs line 51 for "penyl readphenyl column 6, lines 60 to 62, for the upper portion of the formulareading Signed and sealed this 25th day of July 1961.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents

5. A DYESTUFF OF THE FORMULA: